CN107640822A - A kind of hydrophilically modified method of plastic filler surface grafting anti-agglomeration - Google Patents
A kind of hydrophilically modified method of plastic filler surface grafting anti-agglomeration Download PDFInfo
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- CN107640822A CN107640822A CN201610580988.2A CN201610580988A CN107640822A CN 107640822 A CN107640822 A CN 107640822A CN 201610580988 A CN201610580988 A CN 201610580988A CN 107640822 A CN107640822 A CN 107640822A
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- filler
- plastic filler
- agglomeration
- acrylic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a kind of hydrophilically modified method of plastic filler surface grafting anti-agglomeration, comprise the following steps：Untreated plastic filler is put into acrylic acid methanol solution under ultrasound condition and carries out that surface grafting acrylic acid introduces hydrophilic radical and anti-agglomeration is modified, naturally dry obtains product, in the acrylic acid solution solvent be methanol, solute be acrylic acid.The hydrophilically modified method of plastic filler surface grafting anti-agglomeration of the present invention is set about from the modification of filler, under ultrasound condition, hydrophobicity according to filler surface, hydrophilic radical is introduced in filler surface grafting acrylic acid, the hydrophilicity on filler surface, microorganism is improved in the speed of growth on filler surface, adhesion amount and improves the growth structure of biological flora so as to improve biomembrane to sewage and the treatment effect of waste water.The hydrophily and surface anti-agglomeration of plastic filler can be improved by being immersed in plastic filler i.e. under ultrasound condition in the acrylic acid solution of different temperatures, time, concentration, and method of modifying of the present invention for improving plastic filler surface grafting anti-agglomeration.
Description
Technical field
The present invention relates to the hydrophilically modified method of filler surface grafting anti-agglomeration, more particularly under ultrasound condition,
The method of modifying that grafted propylene acid introduces hydrophilic radical and anti-agglomeration is carried out to undressed common plasticses filler surface, especially
It is that conventional method can be avoided the phenomenon reunited occur to filler surface after plastic filler surface hydrophilicity graft modification, mainly
Modification for biofilm reactor filler.
Background technology
Biofilm reactor is to add various fillers in the reactor so that attached growth of microorganisms makes to be formed on filler
The reactor for the structure similar to film that one layer of biology is formed.At present, the technology should in sanitary sewage, Industrial Wastewater Treatment
With relatively extensively.
Filler is one of principal element for influenceing biofilm reactor water treatmenting performance, is classified from material, filler is divided into
Polyethylene, polypropylene, polyvinyl chloride, polyurethane and ceramics etc.；Classify from configuration, there is Pall ring, polyhedron empty ball and K3 etc.
Form.
Modification both at home and abroad to filler at present is concentrated mainly on filler hydrophily, surface charging property, bioaffinity and is modified
Etc. several aspects.
Stuffing surface modification refers to that carrying out processing to filler surface by some methods physically or chemically makes its superficiality
It can be improved, to improve such as hydrophily, biocompatibility on filler surface.The side of stuffing surface modification from principle
Method includes chemical method and Physical, and chemical modification method, which refers to, to be added some materials on filler surface and it is passed through hair on filler surface
To improve the modification technology of the performance on filler surface such as hydrophily or compatibility, physical modification method refers to pass through for biochemical reaction
Physical process changes the performance such as hydrophily and compatibility on filler surface.Conventional stuffing surface modification method, which mainly has, comes to the surface
Learn modification, surface physics cladding, plasma surface treatment method, mechanically modifying and surface graft modification etc..
Surface grafting is one of main method that surface modification is carried out to organic high molecular polymer, and surface grafting will can have
The macromolecular for having difference in functionality structure is covalently bound to material surface, material is produced new physical and chemical performance.Surface grafting
It is homogeneous reaction, is primarily due to graft copolymerization and occurs to involve each macromolecular of material surface in the liquid phase.It is right
When polymer surface carries out graft modification, there is the property of material in itself to be kept for the advantages of constant.
But after filler carries out surface grafting, filler surface can produce agglomeration.Existing document report ultrasound wave energy is effective
Promote the progress that acrylic acid is reacted Solid-Phase Grafting of Methyl-Methacrylate and grafting rate can be improved.
Existing plastic filler has as a drawback that：Plastic filler surface is in hydrophobicity, makes it in bio membrane process
The biofilm cycle is long, influences microorganism in the growth conditions and adhesion amount on film surface, the growth structure of biological flora and microorganism
Film is bad to the treatment effect of waste water.
The content of the invention
The purpose of the present invention be exactly in order to overcome and solve existing plastic filler surface in hydrophobicity, make it in biomembrane
The biofilm cycle is long in handling process, influences microorganism in the growth conditions and adhesion amount on film surface, the growth structure of biological flora
And microbial film to the treatment effect of waste water the problem of and easily roll into a ball after carrying out surface graft modification to filler by ultrasound
Poly- problem.
For disadvantage mentioned above and problem, research is invented the plastic filler surface graftings such as a kind of conventional polyethylene, polypropylene and prevented
The modified preparation method of reunion, it sets about from the modification of filler, according to the hydrophobicity on filler surface, introduces hydrophilic radical, so as to
Improve the hydrophilicity on filler surface, i.e., be grafted plastic filler to plastic filler in ultrasound condition, acrylic acid-methanol solution
Acrylic acid introduces hydrophilic radical, and the present invention is used to improve plastic filler surface hydrophilic performance and filler surface grafting changes
Property after easily agglomeration traits method.
The hydrophilically modified method of plastic filler surface grafting anti-agglomeration, comprises the following steps：By plastic filler in ultrasound
Under the conditions of be put into acrylic acid-methanol solution carry out surface grafting anti-agglomeration it is hydrophilically modified, naturally dry obtains product, described
Ultrasound refers to carry out that plastic filler surface grafting anti-agglomeration is hydrophilically modified, methanol is propylene sour solvent, propylene under different capacity
Acid selects different molar concentrations.
Plastic filler surface grafting anti-agglomeration of the present invention it is hydrophilically modified, wherein, the concentration of the acrylic acid
For 0.5~5mol/L, ultrasonic power is 40K~100K, the time is 1.5~6h.
The hydrophilically modified method of plastic filler surface grafting anti-agglomeration of the present invention, wherein, the plastic filler
For one or more of mixtures in PP, PE, PVC.
The product that the hydrophilically modified method of plastic filler surface grafting anti-agglomeration of the present invention obtains, i.e. plastics are filled out
Expect surface hydrophilicity method of modifying.
Plastic filler surface grafting anti-agglomeration of the present invention it is hydrophilically modified after filler in sewage disposal
Using.
Application of the present invention, under anoxic conditions, sewage plant processing is carried out using two level MBBR reactors, it is described
MBBR reactors include surface grafting anti-agglomeration it is hydrophilically modified after plastic filler and undressed common plasticses
Filler, intake and continuously enter drainage pattern operation, HRT 6h, media-filling rate for certain municipal wastewater treatment plant reverse osmosis concentrated water, peristaltic pump
For 30%, stir speed (S.S.) is controlled in 60rmin-1, using methanol as supplementary carbon source, dosage 25mgL-1, COD/N ratios=
4.2~5, T=25 ± 1 DEG C.
The hydrophilically modified method difference from prior art of plastic filler surface grafting anti-agglomeration of the present invention is have
There are following advantage and beneficial effect：
(1) measured by research contact angle measurement DSA 30 (German Ke Lvshi KRUSS companies), what the present invention made
Hydrophilic filler is compared than the static contact angle on unmodified plastic filler surface reduces about 56~77%, after the present invention makes
Filler contact angle have and significantly reduce, show that surface hydrophilicity is remarkably reinforced.
(2) observed by using FEL Quanta 200FEG field emission scanning electron microscopes, what the present invention made connects
The filler of branch anti-agglomeration surface hydrophilicity is covered by protrusion in irregular shape, and protrusion uniformly divides on plastic filler surface
Dissipate, surface roughness and surface area increase, during applied to water and wastewater treatment, the roughness and protrusion on surface are uniform
It is scattered to be beneficial to microorganism in the uniform attachment on filler surface and the biofilm speed and microbial biomass of raising filler.
(3) by VG Scientific ESCALab220i-XL types photoelectron spectrographs (U.S.) to the anti-group of surface grafting
It is poly- it is hydrophilically modified after plastic filler surface composition tested, the C element relative amount on unmodified plastic filler surface
About 94~97%, O elements relative amount is that about 2~3%, O/C values are 3.7~3.9%；The plastics made of the present invention are filled out
The C element relative amount for expecting surface is not 64~70%, O element relative amounts are 21~25%, O/C values are 32~39%, and not
Modified plastics filler is compared, and the content reduction of surface C element, the content of O elements rises, O/C values also rise, and makes plastic filler table
Face introduces oxy radical, and hydrophily enhancing, which has been modified mode, can change the ratio of plastic filler surface-element composition.
(4) mainly exist through C spectrograms and O spectrum analysis, untreated plastic filler surface C element in the form of C-C/C-H,
Relative amount 98~100%；The plastic filler surface C element made of the present invention mainly exists in the form of C-O, C in C-C/C-H
Relative amount 25~35%, in C-O C relative amount 54~65%, C relative amount in-C=O/-C-O-O ,-O-C=O
It increased, respectively 0.1~0.2%, the relative amount of C element substantially increases in 5~6%, especially-O-C=O.Not
The plastic filler of processing, to through the plastic filler surface O elements that make of the present invention mainly in the form of-C=O keys and-C-O- keys
In the presence of, the filler that makes of present invention content increase with unmodified filler compared with, the relative amount 8 of O elements in-C=O keys~
The relative amount 4~6% and 10~12% of O elements in 11% ,-C-O- key.
(5) filler is put into membrane bioreactor and tested, the dosing ratio 30% of filler：1. under anoxia condition, change
Packed column reactor after filler after property is more unmodified, which started to the stable time, shortens about 4~5d, modified filler
In system operation three days just it is observed that obvious biofilm phenomenon, and conventional PE fillers are then difficult to observe by obvious biofilm and showed
As.The plastic filler surface that the present invention makes NO compared with3 -- N average removal rate 95~99%, TN average removal rate 70~
78%, untreated plastic filler compares (NO3 -- N average removal rate 60~75%, TN average removal rate 60~68%) effect
It can significantly improve.2. under aerobic condition, the packed column reactor after modified filler is more unmodified started to the stable time
40%~60% is shortened, modified filler is within time of the system operation less than two days just it is observed that obvious biofilm shows
As, and conventional plastic filler is then difficult to observe by obvious biofilm phenomenon.When biofilm reaches stable, modified filler is more not
Modified filler is compared：NH4 +- N average removal rate improve 50%~60%, COD average removal rate improve 30~
45%.
As a result show that surface is modified and not only enhance nitrification, while promote denitrification.
The plastic filler surface hydrophilicity method of modifying of the present invention is described further with reference to specific embodiment.
Embodiment
Embodiment 1
The hydrophilically modified method of plastic filler surface grafting anti-agglomeration, comprises the following steps：Under ultrasound condition, by
Plastic filler after liquid phase oxidation is put into molar concentration 5mol/L acrylic acid-methanol solution and carries out surface graft modification
Afterwards, naturally dry obtains product, and ultrasonic power is 60K, time 1.5h, one kind in plastic filler PP, PE, PVC or
Several mixtures.
Plastic filler surface after being measured by research contact angle measurement DSA30 (German Ke Lvshi KRUSS companies)
Static contact angle reduces about 76%~79%, is seen by using FEL Quanta 200FEG field emission scanning electron microscopes
Examine, filler surface occurs having accumulation material in irregular shape, and surface is covered by protrusion in irregular shape, protrusion group
Poly-, surface area increase；By VG Scientific ESCALab220i-XL types photoelectron spectrographs (U.S.) to unmodified and
Modified plastic filler surface composition is tested, and the C element relative amount on plastic filler surface is about 69~70%, O members
Plain relative amount is about 21~23%, O/C values are about 30~32%, and surface C element is mainly deposited in the form of C-O and relative amount 63
~65%, C relative amount increased in-C=O/-C-O-O ,-O-C=O；Plastic filler surface O elements are mainly with-C
The form of=O keys and-C-O- keys is present, the relative amount 9~11% of O elements in-C=O keys, and O elements is relative in-C-O- keys
Content 11~13%；During applied to water and wastewater treatment, under anoxic conditions, when biofilm reaches stable, NO3 -- N and TN
Clearance improve a lot；Under aerobic condition, COD and NH4 +- N clearance improves a lot.
Embodiment 2
Difference from Example 1 is：The power of ultrasound is 40K, time 6h, and other are the same as embodiment 5.
Embodiment 3
Difference from Example 1 is：Time is 6h, and the molar concentration of acrylic acid is 1.5mol/L, and other are the same as implementation
Example 5.
Embodiment 4
Difference from Example 1 is：The power of ultrasound is 100K, time 6h, and the molar concentration of acrylic acid is
1.5mol/L, other are the same as embodiment 1.
The product that the hydrophilically modified method for the plastic filler surface grafting anti-agglomeration that the present invention makes obtains, i.e., it is modified
Hydrophilic plastic filler, modified hydrophilic plastic filler is applied in sewage disposal, including aerobic condition and anoxic bar
Part.
Citing：Under anoxic conditions, sewage disposal is carried out using MBBR reactors, with the plastic filler that makes of the present invention and
Common plastic filler, intake and continuously enter drainage pattern operation for Beijing's sewage plant tail water (water outlet), peristaltic pump, HRT is
6h, media-filling rate 30%, stir speed (S.S.) are controlled in 60rmin-1, using methanol as supplementary carbon source, dosage 25mg
L-1, COD/N ratios=4.2~5, T=25 ± 1 DEG C.
Under anoxia condition, within the experiment starting period, the plastic filler that the present invention makes is to NO3 -- N average removal rate exists
More than 80.0%, to TN average removal rate about 40%；When the plastic filler biofilm that the present invention makes reaches stationary phase
Between shorten about 4d.Within experiment stationary phase, untreated plastic filler is to NO3 -- N average removal rate is 82.6%；This hair
The plastic filler of bright making is to NO3 -- N average removal rate is 98.1%.Modified filler just can be seen for three days in system operation
Obvious biofilm phenomenon is observed, and untreated plastic filler is then difficult to observe by obvious biofilm phenomenon.
(processing method is using conventional processing method), the plastic filler reactor start-up that the present invention makes under aerobic condition
40%~60% is shortened to the stable time, the plastic filler that the present invention makes is within time of the system operation less than two days
Just it is observed that obvious biofilm phenomenon, and untreated plastic filler is then difficult to observe by obvious biofilm phenomenon.Biofilm reaches
To when stablizing, the more untreated plastic filler of plastic filler that the present invention makes is compared：NH4+-N average removal rate improves
50%~60%, COD average removal rate improve 30~45%.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made, it all should fall into the protection domain of claims of the present invention determination.
Claims (6)
- A kind of 1. hydrophilically modified method of plastic filler surface grafting anti-agglomeration, it is characterised in that：Comprise the following steps：Under ultrasound condition, undressed plastic filler is put into acrylic acid solution (solvent is methanol) and carries out surface hydrophilic Property be modified, naturally dry obtains product.
- 2. plastic filler surface hydrophilicity method of modifying according to claim 1, it is characterised in that：The acrylic acid rubs Your concentration is 0.5~5mol/L, and ultrasonic power is 40~100K, the time is 1.5~6h.
- 3. the hydrophilically modified method of the plastic filler surface grafting anti-agglomeration according to claim 1 and claim 2, its It is characterised by：The plastic filler is one or more of mixtures in PP, PE, PVC.
- 4. the hydrophilic plastic filler in claims 1 to 3 described in any one claim is grafted in ultrasound condition lower surface The product that acrylic acid is introduced obtained by hydrophilic radical, i.e., modified anti-agglomeration hydrophilic plastic filler.
- 5. application of the modified anti-agglomeration hydrophilic plastic filler in black water processing described in claim 4.
- 6. application according to claim 5, it is characterised in that：Under anoxic conditions, city is carried out using MBBR reactors Sewage plant tail water (water outlet) processing, hydrophily of the filler including surface grafting anti-agglomeration changes in the two level MBBR reactors Plastic filler and undressed common plasticses filler after property, intake and continuously enter for Beijing's sewage effluents, peristaltic pump Drainage pattern is run, and hydraulic detention time (HRT) is 6h, and media-filling rate 30%, stir speed (S.S.) control is in 60rmin-1, Using methanol as supplementary carbon source, dosage 25mgL-1, COD/N ratios=4.2~5, T=25 ± 1 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582351A (en) * | 2021-07-21 | 2021-11-02 | 浙江桃花源环保科技有限公司 | Water treatment bioreactor based on layered structure |
| CN114590886A (en) * | 2022-02-21 | 2022-06-07 | 中国科学院合肥物质科学研究院 | Self-degradable biological film filler and preparation method and application thereof |
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| CN1350984A (en) * | 2001-10-31 | 2002-05-29 | 华南理工大学 | Process for preparing hydrophilic elastic plastic filler for treating water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582351A (en) * | 2021-07-21 | 2021-11-02 | 浙江桃花源环保科技有限公司 | Water treatment bioreactor based on layered structure |
| CN114590886A (en) * | 2022-02-21 | 2022-06-07 | 中国科学院合肥物质科学研究院 | Self-degradable biological film filler and preparation method and application thereof |
| CN114590886B (en) * | 2022-02-21 | 2023-09-05 | 中国科学院合肥物质科学研究院 | Self-degrading biological film filler and preparation method and application thereof |
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